Catalytic process



i atented Apr. i0,

UNITED STATES PATENT omcs 2,;4830 g r to E. I du P0111; de

mington, Delr, a corporation of g ,N o V jcompaiiiapwu- Delaware No Drawing. ipplicationnilune 1 9.50,

, Serial No. 170,699

8 claims.

of icarbocyclic compounds involve the use of acidic catalysts. Such methods, in general, bring mehts of the rfsulting ring substituted alkyl groups introduced in the alkylation step. More recently (U. 'S. Patent 2,448,641), a new method hasfb'ee'n disc vered for the alkylation of cyclic unsaturated hydrocarbons with olefins by heating'the cyclic unsaturated hydrocarbon with the desired 'monolefimc hydrocarbon at temperatures from 1-50 to 450 Q; under superatrnospheric pressures in the presence of 0.1 to 20% of analkali metal as catalyst, based on the weight of the cyclic unsaturated hydrocarbon.

Although the method of Patent 2,448,641, works well, it has the disadvantage of requiring elevated operating temperatures, which, in conjunction with the required superatmospheric pressures, necessitate the use of the extremely expensive type of equipment needed to withstand these high pressures at the elevated tempera tures, Furthermore'the high operating tempera ture conditions make the process more 'expensive as well as inconvient and undesirable, especially with regard to continuous operations.

It is an objectof this invention to providea novel method for alkyl'ating certain cyclic unsaturated hydrocarbons with monoolefins. A further object is to provide a novel catalytic alkylating certain cyclic unsaturated hydrocarbons with monoolefins at relatively low temperatures. A still further object is to provide a catalytic method for the preferential alkylation in the side chain of alkyl substituted aromatic hydrocarbons and of hydroaromatic compounds, such as cyclohexene, to the nuclear double bond. Other objects will appear hereinafter.-

The objects of this invention are accomplished by the following invention of a process which comprises bringing into contact ma reaction zone and reacting, at a temperature of to 130 C.

under superatinospheric pressure of 100 to 3060 atmospheres in the presence of an 'org'ano-alkali metal catalytic compound, a monolefimchydrocarbon with a cyclic unsaturatedhydrocarbon wherein the unsaturation is present solely in the and which cyclic unsaturated hydrocarbon contains at least one hydrogen atom directly on methylene carbonsalpha 2 attached to a saturated earbon atom which is singly bonded to a ring carbon atom whichin turn is deubly bonded to one cribs adjacent fine carbon atoms. I I

It has now been found that cyclic unsaturated hydrocarbons containing at least one hydrogenbearing, saturated carbon singlybonded to a be alkylate'd on fsai'd saturated, carbon b'y reaef ti'onwit'h at least one monoclefihic, hydrocarbon at temperatures fromj0 C. to'13'0 0., preferably from 35 to under superatmospheri'c pres sure' prefer'ably from 1:00 to 3000 atmospheresor n a ssi l b9 ll c1e ,7 ne h o e b ari a sa iae jcai bq sai nu a'r carbon-being doubly bondedto one of its ish q in 'b n y r n The reactants may be brought into mutual contact in a reaction zone in any order of adbaficH-Wi op elatibh Of invention.

-A pressure resistant reaction vessel is charged with the desired eyclic unsaturated hydrocarbon and 'organo-alkaH metal catalytic order top'revent entrance of air, the charging is usually conducted under a blanketof inert gas. Alternatively, the reacti'on charge can be pressured into the closed and previously evacuated reactionvessel. The vessel is then closed and evacuated, if this has not already been done, placed ina shaker machine, providedwith a heater, and co @ected to a; reservoir Osmond co tro lin m recording merino bottles are placed in position, the vessel" siesrbon atleast' 1c hydrocarbloh or mixtures .thereof'under 'sured to the desired point with the monoolefinic hydrocarbon being used, and heating and agitation started.

The course of the reaction may be followed by the pressure drop due to utilization of the monoolefinic hydrocarbon. The pressure may be maintained inthe desired range by anyone of the several means, such as, by intermittent addition of the monoolefinic hydrocarbon from high pressure storage as needed, or by injecting further quantities of the cyclic unsaturated hydrocarbon, or by injecting a mixture of the mono-v olefinic hydrocarbon and the cyclic unsaturated hydrocarbon preferably under pressure. At the end of the reaction, which is determined by a cessation of pressure drop, the vessel is cooled, bled to atmospheric pressure, opened and the reaction mixture discharged. The catalyst is separated by filtration in those instances soluble and the products isolated by known means, usually by fractional distillation.

The following exam'plsiin which the parts given are by weight and the boiling points are at atmospheric pressure, serve to illustrate and not to limit the process of this invention.

Example I A stainless steel, high pressure reactor or internal capacity corresponding to 400 parts of water is charged with 9 parts of benzylsodium and 87 parts of freshly distilled toluene. The reactor is then closed, flushed with nitrogen, and connected to a source of ethylene under pressure. The reactor is heated to 60 C. and maintained at this temperature for a periodof 16 hours under a pressure of 200 atmospheres of ethylene. This pressure is maintained during the reaction period by intermittent pressuring with ethylene as needed. At the end of this time, the reactor is cooled to room temperature, bled to atmospheric pressure, opened and the reaction mixture removed. Upon fractional distillation, unreacted toluene is removed, B. P. 109-111 C. Continued fractionation yields 41 parts (36.4% yield) of npropylbenzene, B. 1?. 155 to 160 C., 11. 1.4887 and 40.2 parts (35.6% yield) of 3-phenylpentane, B. P. 183 to'186" C., 15, 1.4859.

Another experiment carried out in the same general fashion at an operating temperature of 38C. and under a pressure of 140 atmospheres of ethylene produces 3.6 parts (3.2%) of n-propylbenzene, 11 1.4890.

Example 11 wherein itis in- I pressure, opened and hours under a pressure of 200 atmospheres of ethylene. At the end of this time, the reactor is cooled to room temperature, bled to atmospheric pressure, opened and the reaction mixture removed. The petroleum ether reaction medium and unreacted toluene are removed by fractional.

distillation. Continued fractionation yields '44 parts (38.8% yield) of n-propylbenzene, B. P. 155 to 160 C.

Another similar experiment carried out in the same general fashion except that the operating temperature is 55 C. and the operating pressure is 315 atmospheres of ethylene produces available commercially. Such contaminants may corresponding saturated hydrocarbons ene under pressure.

Example III A stainless steel reactor similar to that described in Example I is charged with parts of toluene, 10 parts of metallic sodium and four parts of diphenylmercury, the latter two reactants rorming the organo-sodium catalyst, phenylsodium, in situ. The reactor is closed, flushed with nitrogen and connected to a source of ethyl- The reactor is then heated to 65 C. and maintained at this temperature for 16 hours under a pressure of 350 atmospheres of ethylene. At the end of this time, the reactor is cooled to room temperature, bled to atmospheric the reaction mixture removed. The unreacted sodium is removed by filtration, diphenylmercury and any by-product mercury are removed by filtration. Unreacted toluene is removed from the reaction mixture by fractional distillation. Continued fractionation yields 8.8 parts (6.7% yield) of n-propylbenzene, B. P. to 158 C.

As pointed out herein, it is necessary to carry out the process of this invention under superatmospheric pressures; hence, the operating equipment will include the normally used pressure resistant reaction vessels equipped with agitators, if desired, and heating elements, aswell as pumps, compressors and'the like for attaining the desired reaction pressures. If desired, particularly. in the case of continuous operations, other pumps or injectors may be provided for adding solutions or suspensions of the organoalkali compound catalyst or additional cyclic unsaturated hydrocarbons to The aromatic and hydroaromatic hydrocarbons used in the process of this invention are those having at least one hydrogen on a saturated carbon which is directly attached by a single bond to a nuclear carbon atom which, in turn, is-

ene, cyclohexene, 3-methylcyc1ohexene-1, 3-ethylcyclohexene-l, 3-propylcyclohexene-l, 9,10-dihydrophenathrene, diphenylmethane, phenylcyclohexylmethane, 1,2-dihydrobenzene, lA-dihydrobenzene, cyclopentadiene and the like.

Suitable examples of the nonoolefinic hydrocarbons, that is olefinic hydrocarbons wherein the sole unsaturation is a single ethylenic double bond, which can be used in the invention are ethylene, propene-l, butene-l, butene-Z, octene-l, octene-2, and the like, particularly those monoolefinswhich contain a. terminal methylene group. The process of this invention is particularly outstanding when applied to the lower monoolefins of up to six carbons, particularly those which are normally gaseous.

The monoolefins may contain small amounts of contaminants normally encountered in them as include the such as ethane, propane and the like, nitrogen, hydrogen, carbon dioxide or oxygen. However,

oxygen in concentrations above 1,000 parts pere million is detrimental to the reaction. Conse purified to contain less than quently, monoolefins 100 parts per million, generally less than 50 parts per million, and preferably less than 10 parts per 34.5 75 million are employed. The monoolefins may be;

the reaction zone. v

process of this carbon atoni which in turn is doubly bonded to one of its adjacent ring carbon atoms.

3. A process for the preferential alkylation of cyclic unsaturated hydrocarbons as set forth in claim 2 wherein said hydrocarbo-alkali metal catalytic compound is an alkali metal alkyl catalytic compound.

4. A process for the preferential alkylation of cyclic unsaturated hydrocarbons as set forth in claim 2 wherein said hydrocarbo-alkali metal catalytic compound is an alkali metal aryl caalytic compound.

5. A process for the preferential alkylation of cyclic unsaturated hydrocarbons as set forth in claim 2 wherein said hydrocarbo-alkalimetal catalytic compound is an alkali metal aralkyl catalytic compound.

6. A process for the preferential alkylation in the side chain of alkyl-substituted aromatic hydrocarbons which comprises bringing into contact in a reaction zone and reacting, at a temperature of 35 to 70 C. under superatmospheric pressure of 150 to 1000 atmospheres in the presence of a hydrocarbo-sodium catalytic compound, a monoolefinic hydrocarbon with an alkyl-substituted aromatic hydrocarbon wherein the unsaturation is present solely in the ring and which contains at least one hydrogen atom directly attached to a saturated carbon atom 8 which is singly which is in turn doubly bonded to one of its adjacent ring carbon atoms.

7. A process for the preferential alkylation in the side chain of alkyl-substituted aromatic hydrocarbons which comprises bringing into contact in a reaction zone and reacting, at a temperature of to C. under superatmospheric pressure of to 1000 atmospheres in the presence of a hydrocarbo-sodium catalytic compound, ethylene with an alkyl-substituted aromatic hydrocarbon wherein the unsaturation is present solely in the ring and which contains at least one hydrogen atom directly attached to a saturated carbon atom which is singly bonded to a ring carbon atom which is in turn doubly bonded to one of its adjacent ring carbon atoms.

8. A process for the preferential alkylationin the side chain of alkyl-substituted aromatic hydrocarbons which comprises bringing into contact in a reaction zone and reacting, at a temperature of 35 to 70 C. under superatmospheric pressure of 150 to 1000 atmospheres in the presence of a hydrocarbo-sodium catalytic compound, ethylene with toluene.

ERNEST L. LITTLE, JR.

No references cited.

bonded to a ring carbon atom- 

1. A PROCESS FOR THE PREFERENTIAL ALKLYATION OF CYCLIC UNSATURATED HYDROCARBONS WHICH COMPRISES BRINGING INTO CONTACT IN A REACTION ZONE AND REACTING, AT A TEMPERATURE OF 0* TO 130* C. UNDER SUPERATMOSPHERIC PRESSURE OF 100 TO 3000 ATMOSPHERES IN THE PRESENCE OF AN ORGANO-ALKALI METAL CATALYTIC COMPOUND, A MONOOLEFINIC HYDROCARBON WITH A CYCLIC UNSATURATED HYDROCARBON WHEREIN THE UNSATURATION IS PRESENT SOLELY IN THE RING AND WHICH CONTAINS AT LEAST ONE HYDROGEN ATOM DIRECTLY ATTACHED TO A SATURATED CARBON ATOM WHICH IS SINGLY BONDED TO A RING CARBON ATOM WHICH IS IN TURN DOUBLY BONDED TO ONE OF ITS ADJACENT RING CARBON ATOMS. 